1. Field of the Invention
The invention relates to the methods for making catalytically effective vanadium/propylene glycol complexes.
2. Prior Art
A process for the manufacture of substituted epoxides from alpha olefins such as propylene styrene, etc., was reported by John Kollar in the 1960's. His U.S. Pat. No. 3,351,635 teaches that an organic epoxide compound can be made by reacting an olefinically unsaturated compound with an organic hydroperoxide in the presence of a molybdenum, tungsten, titanium, columbium, tantalum, rhenium, selenium, chromium, zirconium, tellurium or uranium catalyst.
Kollar's U.S. Pat. No. 3,350,422 teaches a similar process using a soluble vanadium catalyst. The patent teaches the use of hydrocarbon soluble vanadium compounds such as the naphthenates, stearates, octoates, carbonyls, etc., and also the use of chelates and enol salts such as acetoacetonates. It is recommended that a basic substance such as an alkali metal or alkaline earth metal compound (e.g., sodium naphthenate, potassium stearate, sodium or potassium hydroxides, alkoxides, etc.) be used with the vanadium catalysts to improve their efficiency.
Chan-Cheng Su et al. in an article entitled "Metal Ion Catalysis of Oxygen-Transfer Reactions--Vanadium and Molybdenum Chelates as Catalysts in the Epoxidation of Cycloalkanes" (Inorganic Chemistry, Vol. 12, No. 2, 1973, pp. 337-342) disclose the use of soluble vanadium compounds such as vanadyl acetylacetonate, vanadyl bis(dipivaloylmethide), vanadyl hexafuoroacetyacetonate, etc. The article reports that benzene solutions deteriorated on standing for several hours.
Gould et al. in an article entitled "Metal Ion Catalysis of Oxygen Transfer Reactions" (Journal of the American Chemical Society, Aug. 1968, 90:17, pp. 4573-4579), disclose the reaction of tert. butyl hydroperoxide with cyclohexene in the presence of vanadium acetylacetonates and vanadium octoate. The authors noted that the solutions showed deterioration on standing.
In U.S. Pat. No. 4,434,975 to ARCO, investigators found that molybdenum catalysts could be made from saturated alcohols or glycols having one to four carbon atoms, such as ethylene glycol and propylene glycol, by reacting them with molybdenum metal and an organic hydroperoxide, peroxide, or H.sub.2 O.sub.2. Molybdenum compounds prepared by reacting an ammonium-containing molybdate with a hydroxy compound, for example, an organic primary or secondary alcohol, a glycol or a phenol, are described in U.S. Pat. Nos. 3,784,482 and 3,787,329 to Cavitt.
Further, U.S. Pat. No. 3,573,226 to Sorgenti discloses that molybdenum-containing epoxidation catalyst solutions may be made by heating molybdenum powder with a stream containing unreacted tertiary butyl hydroperoxide and polyhydric compounds of from about 200 to 300 molecular weight and having from 4 to 6 hydroxyl groups per molecule. These catalysts are used for the epoxidation of propylene according to U.S. Pat. No. 3,666,777 to Sorgenti.
U.S. Pat. No. 3,953,362 to Lines et al. reveals that novel molybdenum epoxidation catalysts may be prepared by reacting an oxygen-containing molybdenum compound with hydrogen peroxide and an amine and optionally water or an alkylene glycol at elevated temperatures. Similar catalysts are prepared by reacting an oxygen-containing molybdenum compound with an amine and an alkylene glycol at elevated temperatues according to U.S. Pat. No. 4,009,122 also to Lines et al.